EP0329603B1

EP0329603B1 - Grain boundary junction devices using high-tc superconductors

Info

Publication number: EP0329603B1
Application number: EP89810047A
Authority: EP
Inventors: Praveen Chaudhari; Cheng-Chung John Chi; Duane Brian Dimos; Jochen Dieter Mannhardt; Chang Chyi Tsuei
Original assignee: International Business Machines Corp
Current assignee: International Business Machines Corp
Priority date: 1988-02-16
Filing date: 1989-01-19
Publication date: 1992-07-08
Also published as: US5162298A; JPH0828536B2; EP0329603A3; JPH01218077A; DE68901980D1; US5278140A; DE68901980T2; EP0329603A2

Description

This invention relates to devices employing high-T_c superconducting materials, and more particularly to simple, practical devices employing these materials, and to methods for making these devices. The devices are planar structures employing selected grain boundaries in the high-T_c superconducting materials as weak link or junction barriers. Such structures are reproducibly made with good operating margins.
Recently, the remarkable discovery by J.G. Bednorz and K.A. Müller, reported in Z. Phys. B. - Condensed Matter 64, 189 (1986) and Europhysics Letters, 3, 379 (1987) completely changed the direction and importance of superconducting technology. Their discovery was that certain metallic oxides can exhibit superconducting transition temperatures considerably in excess of 23K. These materials are often termed "High-T_c Superconductors". Since the initial discoveries of Bednorz and Mueller, a vast amount of research and development has been undertaken around the world to further study these types of superconducting materials in order to extend even farther the temperature range over which the materials are superconducting, as well as to understand the basic mechanisms for superconductivity in this class of materials.
sp. Bednorz and Müller first showed superconducting behavior in mixed copper-oxides, typically including rare earth and/or rare earth-like elements and alkaline earth elements, for example La, Ba, Sr, ..., and having a perovskite-like structure. Materials including the so called "1-2-3" phase in the Y-Ba-Cu-O system have been found to exhibit a superconducting transition temperature in excess of 77K. R.B. Laibowitz and co-workers were the first to achieve and describe a method for making thin films of these materials. These thin film structures and methods for making them are described in Phys. Rev. B, 35, 8821 (1987). In this technique, a vapor transport process is used in which the components of the superconducting film are vaporized and deposited on a substrate in an oxygen atmosphere, after which the deposited film is further annealed.
Another paper describing thin films of these high-T_c superconductors, and specifically high critical currents in these materials, is P. Chaudhari et al., Phys. Rev. Lett. 58, 2864, June 1987. Chaudhari et al. described epitaxial high-T_c superconducting films formed on substrates such as SrTiO₃, in which the critical current at 77K was in excess 10⁵ A/cm².
Other references generally describing the deposition of films or layers of high-T_c superconducting materials include EP-A-0 288 711 and EP-A-88810600.2. The first of these references describes a plasma spray coating process while the second describes a method for coating a substrate, as by spraying from solution, and then patterning the coated film to eventually produce a patterned layer of high-T_c superconducting material.
Epitaxy of high-T_c superconducting films has been accomplished on several substrates, including SrTiO₃. In particular, superconducting films capable of carrying high critical currents have been epitaxially deposited as noted in a paper by P. Chaudhari et al., published in Physical Review Letters, 58, 2684, June 1987.
The initial work of Bednorz and Müller has been extended to include other copper oxide compositions which exhibit high temperature superconductivity. These other compositions typically do not include a rare earth element, but instead include an element such as Bi. A representative material is one in the system Bi-Sr-Ca-Cu-O which exhibits a drop in electrical resistance at about 115K and a transition to zero resistance at 80K. Recently, C. Michel and co-workers reported superconductivity in the non-rare earth containing BiSrCuO system with transition temperatures as high as 22K, cf. C. Michel et al., Z. Phys. B-Condensed Matter, 68, 412 (1987). A new BiSrCaCuO_x composition was then found by Maeda and Tanaker to exhibit high transition temperatures with a resistivity completion in the 80K range and a well defined resistivity decrease at about 115K. This work was reported by these authors in a preprint, which is to be published in the Japanese Journal of Physics.
The copper oxide superconducting materials exhibiting transition temperatures in excess of about 30K are generally known as "high-T_c superconductors", and will be referred to in that manner throughout the specification. This designation is meant to include both the materials having rare earth or rare earth-like elements in their crystalline structure, as well as the more recently reported materials which do not contain rare earth or rare earth-like elements. Generally, all these materials are copper-oxide-based superconductors having Cu-O planes that appear to be primarily responsible for carrying the supercurrents, where the copper oxide planes are separate or in groups separated by the other elements in the compositions.
The advent of high temperature superconductivity should lead to numerous applications of junction devices operating at temperatures much high than those that have been achieved with superconducting devices fabricated from conventional superconductors. However, fabrication of workable devices has not been easy. The first such report of an operable device, in this situation a SQUID device described by R. Koch et al., utilized a film of high-T_c superconductor in which high energy beams were used to produce two localized constrictions to form weak link connectors between high-T_c superconductors. In this manner, a superconducting loop having weak link regions was created and operated successfully as a SQUID. This first high-T_c superconducting device and the method for making it are described in EP-A-0 286 891. Although it has been experimentally established that high-T_c superconducting copper oxides, such as YBa₂Cu₃O_7-x can be reproducibly prepared as thin films, a well defined, all high-T_c single junction exhibiting Josephson tunneling currents has not been successfully fabricated. In such a device, two superconducting layers comprised of high-T_c superconductors are separated by a thin (1 ... 5 nm) layer which operates as a tunnel barrier. An oxide material can be used for the barrier layer. However, the high Tc copper oxide superconductors, whether fabricated as films or bulk samples, require annealing in an oxygen atmosphere at high temperatures, typically about 900°C. This high-temperature processing makes it extremely difficult, if not impossible, to deposit a counter electrode comprised of high-T_c superconducting material over the very thin insulating tunnel barrier. Generally, the high temperature processing severely degrades the junction quality. Such processing is also incompatible with most of the conventional lithographic patterning processes.
Another feature of these high-T_c superconducting materials is their extremely short coherence length, which is a measure of the distance over which the superconducting pairing extends. In these high-T_c superconductors the coherence lengths are typically 1 ... 3 nm, in contrast with coherence lengths of 100 nm in conventional prior art superconducting materials. Such low coherence lengths represent another technical obstacle to making either planar function or weak link type tunnel barriers in, for example, microbridge Josephson junction devices. In weak link devices, a very narrow constriction operates as a weak link barrier between two large superconducting regions to provide Josephson-like characteristics.
However, because the coherence length is so small in high-T_c superconductors, the geometrical constriction must have a dimension of the order of the coherence length in order to exhibit weak-link characteristics. Such narrow constrictions cannot be reliably produced. When planar junctions are formed, it is also very difficult to reliably deposit tunnel barrier layers having thicknesses of the order of the coherence length (about 1 nm) of high-T_c superconductors.
Accordingly, it is a primary object of the present invention to provide a practical device employing high-T_c superconducting materials where the aforementioned problems are avoided.
It is another object of the present invention to provide a method for reproducibly making practical junction and weak-link superconducting devices employing only high-T_c superconducting materials.
It is another object of this invention to provide a device and method for making the device employing high-T_c superconducting materials in a planar configuration wherein the weak-link or junction region can be precisely located with a defined orientation.
In the practice of this invention, junction devices or weak link devices are fabricated using a grain boundary between two high-T_c superconducting grains. These grain boundaries are very narrow (about the order of the unit cell in the materials, i.e., about 1 nm, and their electrical properties (such as resistance) can be readily varied to provide different device properties. In particular, a planar structure is provided utilizing an epitaxial film of high-T_c superconducting material deposited on a substrate having defined and predetermined grain boundaries therein. In this manner, the grain boundaries in the substrate are reproducibly formed in the epitaxial superconductor film. Stated another way, epitaxy maps the polycrystalline structure of the substrate into the high-T_c superconductor film.
It is recognized that grain boundaries have been used to provide potential barriers for the flow of electrons thereacross in prior superconducting devices. Such devices have been called boundary layer Josephson junctions and have been described in the following references:
M. Ito et al., Japanese Journal of Appl. Physics, 21, No. 6, pp. L375-376, June 1982.
M. Ito et al, Appl. Phys. Lett., 43, (3) p. 314, August 1983.
T. Inamura et al, Jap. Journal of Appl. Phys., 21, Supplement 21-1, pp. 313-318, 1982.
The devices described in these references use the grain boundaries that randomly occur when a superconductor film is deposited on a substrate. These superconductors are generally designated BPB films because they are comprised of Ba, Pb, and Bi oxide combinations having a perovskite-type structure. These references do not teach a way to controllably make grain boundary junction devices whose characteristics can be well controlled and which can be reproducibly formed with uniform properties. As noted, these references describe devices in which a random formation of randomly oriented grains occurs in materials having low transition temperatures of about 13K.
In further contrast with these and other references, the devices of the present invention are made in an epitaxial layer of high-T_c superconducting material. Generally, epitaxy is thought of with respect to single crystal material rather than polycrystalline materials of the type used for the substrate and the superconducting film in the devices of this invention.
M. Suzuki et al. describes the formation of planar Josephson-type devices using crystalline layers of BPB in J. App. Phys. 53, (3), p. 1622, March 1982. In this structure, two superconducting layers of BPB are separated by an insulating tunnel barrier comprised of an insulating oxide having the same crystal structure as BPB.
Such device structures have not been possible using high Tc superconducting materials, for the reasons described above with respect to the high temperature processing and very short coherence length in these new superconductors.
Accordingly, it is another object of the present invention to provide practical devices utilizing selected grain boundaries in high-T_c superconducting materials.
It is another object of this invention to provide processing techniques for reproducibly making grain boundary superconductive devices employing high-T_c superconducting materials, wherein the device properties are uniform and wherein the device structures are planar and easily and reproducibly fabricated.
It is another object of this invention to provide improved devices employing high-T_c superconductors, wherein the design of such devices and the techniques for making them effectively utilize features found in nature which may otherwise be considered obstacles.
This invention relates to improved devices utilizing high-T_c superconducting materials and uniform, reproducibly created grain boundaries in such films for the fabrication of the devices. It is recognized that grain boundaries have been utilized in the prior art as tunnel barriers in the work relating to BPB oxides, and that the possible presence of grain boundaries leading to Josephson tunneling currents was mentioned in EP-A-0 286 891 However, the present invention seeks to provide devices and methods for producing these devices which are controllable and reproducible to define grain boundary devices in high-T_c Josephson materials having small coherence lengths. Further, the location, orientation, and number of these new grain boundary devices can be predetermined, and the properties of each of the devices can be adjusted during fabrication.
In a preferred embodiment, a substrate is prepared having at least one grain boundary therein, which grain boundary is to be reproduced in an overlying layer of high-T_c superconductor. The layer of high high-T_c superconductor is then epitaxially deposited on the substrate in order to reproduce in the superconducting layer the grain boundary present in the substrate. This defines the location and orientation of the grain boundary in a controlled manner. After this, the superconducting film is patterned to leave at least one superconducting region on each side of the grain boundary, these superconducting regions being used as electrodes for current flow across the grain boundary. High energy beams or excimer laser ablation can be used to define the superconducting regions that are to function as the electrodes for these superconducting devices. After this, the superconducting regions are electrically contacted and appropriately biased to have current flow across the grain boundary which functions as a potential barrier. A plurality of devices of this type can be arranged in any manner to produce an array of such devices, a SQUID, etc.
These and other objects, features, and advantages will become apparent from the following more particular description in which the preferred embodiments are described by way of example with reference to the attached drawings, in which:

FIGS. 1-4 schematically illustrate a process wherein a grain boundary device is fabricated in an epitaxial layer of high-T_c superconducting material.
FIG. 5 schematically illustrates electrical connections to the device produced by the technique illustrated in FIGS. 1-4.
FIG. 6 is a schematic illustration of a layer of high-T_c superconducting material having two grains A and B separated by a grain boundary. Regions I, II, and III are defined by the dashed lines.
FIG. 7 is an illustration of the layer of high-T_c superconducting material shown in FIG. 6, where different regions I, II and III have been processed in grains A and B to illustrate the invention.
FIGS. 8 and 9A - 9C illustrate electrical properties of the regions I, II, and III shown in FIG. 7. More particularly, FIG. 8 is a plot of critical current I_c versus temperature for the three regions I, II, and III, while FIGS. 9A - 9C illustrate plots of critical current I_c versus applied magnetic field H for the three regions I, II, III, respectively.
FIGS. 10A and 10B illustrate a process for fabricating a SQUID comprised of 2 grain boundary devices in a superconducting loop of high-T_c superconducting material.
FIG. 11 is a plot of critical current I^c versus applied magnetic field H for the SQUID illustrated in FIG. 10B, for three different bias currents.

In the practice of this invention, superconducting devices comprised of a single layer of high-T_c superconducting material can be made in a planar geometry utilizing grain boundaries for tunnel barriers or weak link connections between superconducting grains. In contrast with the prior art, this can be done reproducibly and controllably since the grain boundaries can be produced in the superconducting layers in a manner in which the orientation and location of the grain boundary are predetermined.
The general process steps include the preparation of the substrate having at least one grain boundary defined therein with respect to the orientation and location of the grain boundary. After this, a high-T_c superconducting layer is epitaxially deposited on the substrate (or on a thin interface layer epitaxially grown on the substrate) in order to produce in the superconducting layer a grain boundary corresponding in location and orientation to the grain boundary in the underlying substrate. After this, the superconducting layer is patterned to leave regions of superconducting material on either side of the grain boundary in order to produce a device having superconducting regions (electrodes) separated by the grain boundary. Electrical contacts can then be made to the superconducting regions for connection to appropriate biasing sources. As will be seen, the properties of the grain boundary can be adjusted and multiple devices can be fabricated along a single grain boundary or along several grain boundaries.
Referring more particularly now to FIGS. 1-4, the general technique for producing a planar grain boundary device is illustrated. In this technique, there is no subsequent processing step which would interfere with the material properties of any of the component parts of the device, and the structure that is obtained is planar.
The grain boundary functions as a Josephson tunneling barrier or weak link connection, and is typically about 1 nm in width in these high-T_c superconducting materials. More generally, the grain boundary width is of the order of the unit cell of these high-T_c superconductors. In FIG. 1, substrate 10 includes two single crystal grains A and B separated by a grain boundary GB. This grain boundary is approximately 1 nm in width and is schematically illustrated by the stipled region between the crystalline grains A and B.
In FIG. 2, a layer 12 high-T_c superconducting material has been epitaxially deposited on the substrate 10 using, for example, known techniques. These techniques include vapor deposition as by evaporation or sputtering from multisources as described in the aforementioned articles in the names of R. B. Laibowitz, P. Chaudhari and others. Because the superconducting layer 12 is epitaxially formed on the substrate 10, it will have crystalline regions A and B coextensive with those in the substrate 10, and a grain boundary GB having the same orientation and location as the grain boundary in the underlying substrate 10.
In FIG. 3, the superconducting layer 12 is patterned, for example by using photons or high energy particles, represented by the arrows 14. This patterning can be done in a variety of ways, and is used to define regions of the superconducting layer 12 which are to be left in their superconducting state while the irradiated portions are either physically removed or converted to a nonsuperconducting (i .e., normal) state. In order to render an irradiated region nonsuperconducting, the technique described in EP-A-0 286 891. This technique is more fully described in two publications by G.J. Clark et al., appearing in Appl. Phys. Lett. 51, (1987) at pages 139 and 1462, and comprises the use of high energy beams to cause damage in high-T_c superconducting materials. This damage can change the properties of the material from superconducting to normal and even to a nonsuperconducting, insulating state having an amorphous structure. Examples of high energy beams that can be used for this purpose are directed ion beams comprising ions such as oxygen, As, Kr, etc. The ion beam can be directed to selected areas of the superconducting layer through the use of a mask. An example of a SQUID device made by this technique is described in R. H. Koch et al., Appl. Phys. Lett., 51, p. 200 (1987).
High energy beams providing energies in the range of about 250 keV - 2 or 3 MeV will typically provide enough damage to alter the properties of high-T_c copper oxide superconductors. However, it is within the practice of this invention that patterning can be accomplished by energy beam irradiation where the superconducting material is not totally converted to a nonsuperconducting state, but rather has its critical transition temperature T_c lowered appreciably with respect to the nonirradiated regions of the superconducting layer.
Another technique for patterning high-T_c superconducting layers is the use of excimer ablative photodecomposition in which ultraviolet radiation impinges on the superconducting layer to ablate (i.e., blow away) the irradiated regions.
Ablative photodecomposition will occur if the energy fluence of the UV radiation is sufficiently high that the threshold for ablative photodecomposition is exceeded. In this process, the ablation occurs with substantially no thermal effect to the surrounding nonirradiated regions. This is a particularly good technique, as the surrounding regions will have the same superconducting properties after patterning has occurred.
FIG. 4 illustrates the structure that remains after patterning. Here, a thin strip of the superconductor 12 is left on the substrate 10, the superconductor 12 including grains A and B separated by the grain boundary GB in the superconducting material. As is apparent, it is a planar structure wherein grains A and B can be used for electrical contacts, the current flow being substantially normal to the plane of the grain boundary.
Thus, the general steps of this process include the provision of a substrate having at least one grain boundary therein whose location and crystal orientation are predetermined, the epitaxial deposition of a layer of high-T_c superconducting film on the substrate to establish in the superconducting film a grain boundary corresponding to that in the substrate, patterning of the superconductor to leave superconducting regions separated by a portion of the grain boundary, and contacting the superconducting regions with the appropriate electrical sources. One example of the final structure is shown in FIG. 5.
In FIG. 5, electrical contacts 16 are made to superconducting grains A and B and a bias source, represented by battery 18 is attached thereto for providing a current flow across the grain boundary GB in the superconducting layer.
The substrate materials are selected from those materials on which an epitaxial layer of high-T_c superconducting film can be deposited. Examples of suitable substrates include SrTiO₃ substrates for epitaxial deposition thereon of high-T_c superconducting materials such as YBa₂Cu₃O_7-x. Other suitable substrates will be apparent to those of skill in the art, the substrates being generally chosen to have sufficient lattice match with the desired high-T_c superconducting material that the superconducting material can be epitaxially deposited thereon.
Techniques exist in the art for providing substrates having controlled grain boundary growth. For example, a grain boundary with a controlled misorientation can be obtained by forming a bicrystal from two oriented single crystals. The bicrystal is grown by sintering two single crystal pieces in a powder compact. During sintering, the single crystal pieces grow at the expense of the smaller surrounding grains until the single crystals impinge on each other to form a single grain boundary. This technique has been used to form the bicrystal of SrTiO₃ at a sintering temperature of 1600°C. Alternatively, a bicrystal can be formed by hot pressing two single crystal pieces together. While both techniques can be used to form a long, well-defined grain boundary, the advantage of the second method is the ability to form a straight grain boundary that is free of pores.
As was described, the grain boundary forms a tunneling barrier or weak link between the superconducting grains to which electrical contact is made. The critical current density and tunneling characteristics of the grain boundary can also be modified with a low temperature (less than 400°C) annealing step in a controlled gas atmosphere. Both inert and reducing gasses, such as He and Ar, as well as reactive gasses such as CO₂ are effective for this purpose. An inert gas annealing step acts to reduce the oxygen content of the superconductor film. A CO₂ anneal will promote the formation of BaCO₃ in a film of YBa₂Cu₃O_7-x, where BaCO₃ is an insulator. Since the activation energies for diffusion and solid state reaction of grain boundaries are typically lower than for the rest of the lattice, an optimum set of annealing temperatures and times exist for which the transition temperature T_c and normal state resistivity of the grain boundary are altered while leaving the corresponding properties of the adjacent superconducting grains relatively unaffected.
The principles of this invention were demonstrated by the fabrication of several Josephson junctions using a grain boundary in the high-T_c superconductor YBa₂Cu₃O_7-x. For this, a polycrystalline layer of high-T_c superconductor having a large grain size in the plane of the film was fabricated. This superconducting material was epitaxially grown on a substrate of SrTiO₃. Several substrates of polycrystalline SrTiO₃, having grains as large as 200-300 µm, were used on which the YBaCuO superconducting films were deposited.
These large grain SrTiO₃ substrates were prepared by sintering cold-pressed pellets of fine-grained powder (average grain size approximately 2.5 µm) in air at temperatures in the range 1600-1650°C, for at least 48 hours. These sintering conditions cause exaggerated grain growth to occur, which leads to the formation of very large grains in the dense pellets (ρ/ρ_th ≧ 99%)
The strontium titanate powder was prepared by reacting high purity powders of strontium carbonate and titanium dioxide at 1450°C until a single phase material is obtained.
To fabricate a single Josephson junction containing a well defined grain boundary as the weak-link bridge, high-T_c YBa₂Cu₃ films were epitaxially deposited onto the large grain polycrystalline SrTiO₃ substrates. The details of superconductor film deposition and post deposition annealing are those which have been described previously by R.B. Laibowitz, P. Chaudhari, et al. After this annealing step the superconducting films were epitaxially aligned with the grain orientation of the substrate, resulting in a large-grained superconducting film. This is illustrated in FIG. 6 where the superconducting film 20 is epitaxially aligned with the substrate 22. Large grains A and B are produced in the superconducting film 20, where the grains are separated by the grain boundary GB.
In order to define the geometry and dimensions of a grain boundary junction device and its electrode pads, the technique of laser ablation was used. Grains A and B were patterned by excimer laser ablation as described hereinabove in order to make three lines I, II, and III, as illustrated in FIG. 7. In these examples, the substrate-superconducting film combination was mounted into a computer controlled stepping stage and irradiated with a demagnified image of variable size rectangular aperture. This technique can be used to pattern high T_c superconducting films in dimensions ranging from several centimeters in length to submicron dimensions in width without any degradation in critical temperature T_c and critical current density J_c.
In these examples, three narrow lines I, II, III having dimensions of about 20 µm x 80 µm x 0.5 µm thickness were patterned in superconducting film 20. This step removed the superconducting materials in the irradiated regions. The structure produced is shown in FIG. 7 where line I is totally in grain A, while line III is totally in grain B. However, line II straddles the grain boundary GB. In laboratory demonstrations, the width of the lines was varied from approximately I µm to approximately 2 µm. The length of the line within a grain was approximately 40 µm, while the length of the line crossing the grain boundary was varied between 2 and 40 µm.
The electrical characteristics of the three lines I, II, and III are shown in FIGS. 8 and 9A - 9C. In FIG. 8 the critical current Ic is plotted against temperature for current flow in each of the three lines I, II and III. From this FIG. it is apparent that line II, containing a grain boundary, always has a lower critical current than that lines I and III.
FIGS. 9A - 9C more dramatically illustrate the essential features of a Josephson weak link junction in line II, in contrast with lines I and III. These FIGS. plot critical current Ic versus applied magnetic field H for each of the three lines I, II and III. The plots in FIGS. 9A and 9C are similar, while the plot in FIG. 9B clearly illustrates the presence of the grain boundary junction in line II. The junction resistance here is of the order of a few ohms and its capacitance is estimated to be a fraction of 1 picofarad. The Stewart McCumber parameter is of the order of 1 for these samples. Therefore, the hysteresis in the I-V curves for these samples is quite small, in sharp contrast to the conventional overlap junctions with higher capacitance made by separating two superconducting layers with an insulating layer of, for example, an oxide material.
In the practice of the present invention, the number of grain boundaries, their orientations and their locations in the superconducting layer are known in advance of patterning for device formation. This is a major distinction over the randomness with respect to location and orientation of prior art grain boundary devices using other types of superconductors. Another major distinction is with respect to the superconducting grain size that is used in the present invention in contrast with that of prior art grain boundary devices. In the present invention, the grain sizes are typically hundreds of micrometers, in contrast with an average of about 10 microns grain size for prior art devices. Because the grains in the present invention are very large, it is easy to isolate grain boundaries for patterning and formation of devices. This cannot be achieved in the prior art where the grain boundaries are extremely short and randomly oriented.
Another advantage of the present devices in contrast with prior art grain boundary devices relates to the uniformity of properties along the grain boundaries. In the present invention, long grain boundaries can be produced so that the same grain boundary can be used when patterning several devices, or an array of devices. Since the use of the same grain boundary as a barrier in more than one device helps to ensure the uniformity of individual device properties, the quality of circuits and arrays produced from devices made in accordance with the present invention can be significantly greater than those using prior art structures. For example, in a SQUID device, a superconducting loop is formed including at least 2 weak links or tunnel barriers. In the present invention, it is possible to construct the superconducting loop in such a way that multiple tunnel barriers are formed using the same grain boundary in order to make all the weak link devices in the superconducting loop have essentially identical properties. This cannot be achieved in prior art structures utilizing several grain boundaries.
FIGS. 10A and 10B illustrate a SQUID device that was prepared in accordance with the present invention, while FIG. 11 is a plot of critical current Ic versus applied magnetic field H, for different values of bias current through the SQUID. This plot was made at 4,6K, although the same general characteristics are obtained at temperatures above 77K.
FIG. 10A is a top view of a superconducting layer 24 (on a substrate not shown in this view) having a single grain boundary GB therein separating the superconducting grains A and B. The dashed lines 26 and 28 define the boundaries of the superconducting loop that is to be formed for the SQUID device. Regions of the superconducting layer outside dashed line 26 and inside dashed line 28 were removed by laser ablation to leave a loop of superconducting material 30 (FIG. 10B). This superconducting loop is located on the substrate 32, and includes a first portion 30A and a second portion 30B separated by two grain boundary regions GB. Thus, two tunnel barrier or weak link devices are formed in the superconducting loop 30, thereby producing the SQUID.
FIG. 11 shows the response of the SQUID of FIG. 10B to an applied magnetic field, and is based on measurements made of the device. A current was produced in the superconducting loop and a magnetic field H was applied parallel to the plane of the grain boundaries and perpendicular to the plane of the superconducting layer 24. FIG. 11 shows the interferometer response of the SQUID of FIG. 10B to the applied magnetic flux for three values of bias current I_b, I_b2, I_b3 through the SQUID loop. The precise periodicity and the large modulation depth as a function of magnetic field clearly demonstrates the usefulness of these grain boundary junctions in the fabrication of devices, such as the SQUID of FIG. 10B. In addition, the small B_c (< 1) for these grain boundary junctions eliminates the need for an external resistance shunt to achieve nonhysteretic SQUID operation.
A planar spiral coupling coil comprised of all high-T_c superconducting materials can be made on a separate chip. After individual testing of the coil, the coil and the SQUID of FIG. 10B can be positioned to achieve optimum coupling of magnetic fields from the coil to the SQUID. This provides a device with enhanced sensitivity and reproducibility.
What has been described herein are devices based on the first direct measurements of the critical current of a number of grain boundaries and of their adjoining superconducting grains. The critical current of the boundaries is less than that of the adjoining grains, while the temperature and magnetic field dependence of the critical currents of the grain boundaries indicate that the boundaries are comprised of regions of weak and strong coupling. The grain boundaries can be used to form structures such as SQUIDS and provide a natural way to develop more advanced tunneling structures that can be used for scientific or practical applications.
The structures of this invention can be used to provide enhanced devices for many purposes, including infrared sensors and coherent arrays for detection and transmission of millimeter waves and linear junction arrays for voltage standards. For example, a coherent array can be fabricated from a number of tunnel devices formed using the same grain boundary as the tunnel barrier or weak-link barrier in each device. Since each device can be made very small and have the same properties with respect to the superconducting grains and the grain boundary that is used as the tunnel barrier, coherent arrays having enhanced properties can be envisioned. Further, since the location and orientation of the grain boundaries can be precisely controlled, design layouts for a plurality of these devices are easily realized.
The invention is specifically directed to devices and methods using controlled imperfections (such as grain boundaries) in a superconducting layer where the superconducting layer is preferably a high-T_c superconductor of the type exhibiting a crystalline structure including copper oxide planes.

Claims

1. Grain boundary junction devices, characterized by
a first superconducting electrode comprised of a first grain (A) of a high-T_c superconductor,
a second superconducting electrode comprised of a second grain (B) of a high Tc superconductor,
a grain boundary (GB) located between said first and second superconducting grains (A, B), and providing a potential barrier to the flow of electrons thereacross,
said first and second grains (A, B) being in a single epitaxial layer (12, 24) of high-T_c superconducting material,
said grain boundary (GB) having a plane substantially transverse to the plane of said epitaxial layer (12, 24) of high-T_c superconducting material, and
a crystalline substrate (10, 22, 32) on which said single epitaxial layer (12, 24) of high-T_c superconducting material is epitaxially deposited,
said substrate (10, 22, 32) having a grain boundary (GB) therein which is mapped into said epitaxial superconducting layer (12, 24) and corresponds in location and orientation to said grain boundary (GB) in the overlying epitaxial layer (12, 24) of high-T_c superconducting material.

2. Devices in accordance with claim 1, characterized in that the structure comprising said first and second electrodes separated by said grain boundary (GB) is substantially planar.

3. Devices in accordance with claim 1, characterized in that the high-T_c superconducting material of said layer (12, 24) is a copper oxide material having a superconducting onset temperature greater than 77K.

4. Devices in accordance with claim 3, characterized in that the said superconducting material includes a rare earth or rare earth-like element.

5. Devices in accordance with claim 3, characterized in that the said superconducting material includes an alkaline earth element.

6. Devices in accordance with claim 1, characterized in that said layer (12, 24) of superconducting material includes a plurality of superconducting regions, and that pairs of said regions are located on opposite sides of said grain boundary (GB) in said layer (12, 24), and that electrical means (16, 18) are connected to said pairs of said superconducting regions in said layer (12, 24) for producing electron flow across said grain boundary (GB) in locations therealong defined by each said pair of superconducting regions.

7. Devices in accordance with claim 6, characterized in that said grain boundary has a width of about the order of the unit cell size of said superconducting material, and that said grain boundary forms a weak coupling path between the superconducting regions in each pair of such regions.

8. Devices in accordance with claim 6, characterized in that at least two of said pairs of superconducting regions are electrically separate from one another.

9. Devices in accordance with claim 6, characterized in that at least two of said pairs of superconducting regions are electrically connected in a superconducting loop broken by said grain boundary (GB), thereby forming a SQUID (Fig. 10).

10. Method for making grain boundary junction devices of high-T_c copper oxide superconducting material, comprising the steps of:
providing a crystalline substrate (10, 22, 32) having a grain boundary (GB) therein,
forming a layer (12, 24) of high-T_c superconducting material with a grain boundary (GB) therein having a predetermined location and orientation in said superconducting material,
and which grain boundary (GB) corresponds in location and orientation to the grain boundary (GB) in the underlying substrate,
patterning said superconducting material to electrically isolate two regions therein located on opposite sides of said grain boundary (GB), and providing electrical connections (16) to said superconducting regions to permit the producing of current flow between said regions through said grain boundary (GB).

11. Method in accordance with claim 10, characterized in that at least two high-T_c superconducting regions are connected to form a loop of high-T_c superconducting material having said grain boundary (GB) therein.